Benzoxanthene and benzothioxanthene dyestuffs and process for their manufacture

ABSTRACT

IN WHICH X represents an oxygen or sulfur atom, Y represents   Valuable benzoxanthene and benzothioxanthene dyestuffs of the general formula   D R A W I N G GROUPS, WHEREIN R stands for a hydrogen atom or an alkyl, cycloalkyl or aryl group which may be substituted, a heterocyclic radical, a hydroxyl or amino group, R1 and R2 each represent hydrogen atoms, halogen atoms, especially chlorine or bromine atoms, alkyl or alkoxy groups, and n stands for a number of 1 to 3, which dyestuffs are suitable for dyeing and printing of plastic materials and excellently suitable as fluorescing dyestuffs in the dyeing of condensation resins which when dyed are distinguished by excellent fastness to bleeding and good fastness to light.

United States Patent [191 Troster June 10, 1975 [75] i v t Helmut Troster, Frankfurt am Main, Germany [73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany 221 Filed: Jan. 2, 1973 21 Appl. No.: 320,578

Related US. Application Data [62] Division of Ser. No. 133,351, April 12, 1971, Pat.

[30] Foreign Application Priority Data Apr. 114, 11970 Germany 2017764 [52] US. Cl. 260/281 [51] Int. Cl C07d 39/00 [58] Field of Search 260/281, 282

[56] References Cited lUNlTED STATES PATENTS 1,886,797 11/1932 Eckert 260/281 1,984,110 12/1934 Bodmer 260/281 2,914,531 11/1959 Staeuble 260/281 3,171,843 13/1965 Weissauer 260/281 3,310,564 13/1967 Kasai 260/281 3,322,769 5/1967 Fuchs et a1. 260/282 3,330,834 l /1967 Senshu 260/281 3,349,727 7/1973 Fuchs et al. 260/281 3,357,985 12/1967 Fuchs et al. 260/281 3,367,937 12/1968 Fuchs et al. 260/281 3,376,303 4/1968 Fuchs et a1. 260/281 3,515,732 15/1970 Staeuble et a1. 260/281 X 3,684,729 15/1972 Tuite 260/281 3,741,971 115/1973 Fuchs et a1. 1160/281 3,748,330 7/1973 Fuchs ct al. 260/281 Primary ExaminerDonald G. Daus Attorney, Agent, or Firm-Curtis, Morris & Safford [57] ABSTRACT Valuable benzoxanthene and benzothioxanthene dyestuffs of the general formula 1w ($0 K) X 2 in which X represents an oxygen or sulfur atom, Y represents 7 Claims, N0 Drawings in which X represents an oxygen or sulfur atom, Y represents an oxygen atom or a group, wherein R stands for a hydrogen atom or an alkyl, cycloalkyl or aryl group which may be substituted, a heterocyclic radical, a hydroxyl or amino group, R and R each represent hydrogen atoms, halogen atoms, especially chlorine or bromine atoms, alkyl or alkoxy groups, and n stands for a number of l to 3.

The invention furthermore relates to a process for the manufacture of the above-specified compounds, wherein lbenzoxanthene or benzothioxanthene-3,4- dicarboxylic acid derivatives of the general formula in which X, Y, R and R have the meanings given above, are sulfonated.

The sulfonation may be effected, for example, by treating the compound of formula (2) with concentrated or fuming sulfuric acid at room temperature or at an elevated temperature, the degree of sulfonation being determined by the temperature used, the concentration of the sulfuric acid used and by the reaction time. It is suitable to effect the sulfonation at temperatures in the range of from about 50 to about 170 C using a 95 percent or fuming sulfuric acid having a S content of up to about 20 percent.

The anhydrides or imides of formula (2) used as starting compounds may be obtained according to the process described in German Patent 1,297,259 and French Patent Specification 1,590,506 by heating in the presence of copper or copper salts the diazonium salts of compounds of the formula in which X, Y, R and R have the meanings given above, Z represents a hydrogen atom and Z represents an amino group, or Z, represents an amino group and Z represents a hydrogen atom.

The dyestuffs of the present invention are excellently suited as fluorescing dyestuffs in the dyeing of condensation resins to which they impart luminous greenish yellow to orange yellow shades. The dyeings produced with these dyestuffs are distinguished by excellent fastness to bleeding and good to very good fastness to light. In addition, they are also suitable for the dyeing and printing of plastic materials, for example of polyamides.

The following Examples illustrate the invention:

EXAMPLE 1 28.8 g of benzoxanthene-3,4-dicarboxylic acid anhydride were introduced portionwise into 120 g of fuming sulfuric acid (20 percent SO content). The temperature of the reaction mixture thereby rose to C. The I temperature was then raised within 30 minutes to C and maintained for 30 minutes. After cooling, the sulfonation mixture was poured onto g of ice. After a short time, the luminous yellow sulfonation product of the formula EXAMPLE 2 The sulfonation according to Example 1 was repeated, with the exception that the sulfonation mixture was stirred for 6 hours at l25130 C. The dyestuff of the formula which was isolated in the same manner corresponded with regard to tinctorial behavior largely to that of the afore-mentioned product.

EXAMPLE 3 16.6 g of lO-methoxy-benzoxanthene-3,4- dicarboxylic acid hydrazide were introduced in the manner described in Example 1 into 120 g of fuming sulfuric acid (20 percent S content) and the whole was stirred for 3 hours at 1001 C. After the usual working up, there was obtained the dyestuff of the for- It was found to dye condensation resins, for example toluene-sulfonamide-urea-formaldehyde resins, lumi nous greenish yellow shades having very good fastness properties.

EXAMPLE 4 A mixture of 15.0 g of 9-methylbenzoxanthene-3,4- dicarboxylic acid-N-2,4-dimethylphenylimide and 150 g of 95 percent sulfuric acid were kept for 2 hours at 80 C. After the usual working up, there was obtained the dyestuff of the formula ,CQE H. C

o 1! l I I A 02 T60 3) which dissolved in water gave an intensively green fluorescent solution.

EXAMPLE 5 40.7 g of benzothioxanthene-3,4dicarboxylic acid- NZ,4-dimethylphenylimide were introduced in small portions at 70 C into g of 20 percent oleum and the whole was then stirred for 3 hours at l 10l 15 C. ml of water were then added dropwise at room temperature and the orange sulfonic acid of the formula I /k Q) l 0 1rca ciz a H 1 9 5 a o Err-Q 11' c1 11 2.8 2

9 o ZTOCIL, CH3 CH E 2.,7 2

1o o a-(crz. o 11 a a B 1 1 4 11 o H(CH2}5OCH3 003 a a 1 2 4 12 o )H-CH Br 11 a 1 3 15 o o H H CH5 1 4 1 O A/ 1 i l l l i o O R r i l. Ili' Example 3r fr R a; R; n 14 ll) 0013 E H 1,9 5

l5 l5 0 H H E 1 5 1 16 113 0 c2; CH 1H 1,5 1

17 118 )H l H 11a H 2 5 2 '18 ll 1-r-U +121 1: '31 IE 2,,2 5

. 1133 )ll-H H 1H 5 1.7 i 3 20 111i )rnczr 1i i H E 1 6 3 l l, We claim: n is 2. l. A dyestuff of the formula 3. A dyestuff according to claim 1 wherein X is sulfur, R is 2,4-dimethylphenyl. R and R each is hydrogen. and

l i n is 2. R l/ N 4. A dyestuff according to claim 1 wherein l i X is oxygen, y M L R is n-butyl,

BK k Q, 40 R and R each is hydrogen, and M" K D n is 1.9. i 5. A dyestuff according to claim 1 wherein X is oxygen, R is 3-methoxy-n-propyl, R th ara to X, wherein X is oxygen or sulfur, R 15 hydrogen, amino, zt ggg and lower alkyl, cyclohexoxy lower alkyl, lower alkoxylower alkyl, phenyl, chlorophenyl, lower alkyl phenyl, A dyestuff according to claim 1 wherein di-lower alkyl phenyl, R and R each is hydrogen, ehlo- X is Sulfur rine, bromine, lower alkyl or lower alkoxy, and n is a R R1 and 11 h is hydrogen and value from l lo 3. 5O

7. A d st ffa c din to claim 1 wherein 2. A dyestuff according to claim ll wherein X is fi C or g X Oxygen R is methyl, R H R and R each is hydrogen, and R is methoxy para to X, n is L6. R is hydrogen. and 

1. A DYESTUFF OF THE FORMULA
 2. A dyestuff according to claim 1 wherein X is oxygen, R is -NH2, R1 is methoxy para to X, R2 is hydrogen, and n is
 2. 3. A dyestuff according to claim 1 wherein X is sulfur, R is 2,4-dimethylphenyl, R1 and R2 each is hydrogen, and n is
 2. 4. A dyestuff according to claim 1 wherein X is oxygen, R is n-butyl, R1 and R2 each is hydrogen, and n is 1.9.
 5. A dyestuff according to claim 1 wherein X is oxygen, R is 3-methoxy-n-propyl, R1 is methoxy para to X, R2 is hydrogen, and n is 1.2.
 6. A dyestuff according to claim 1 wherein X is sulfur, R, R1 and R2 each is hydrogen, and n is 1.7.
 7. A dyestuff according to claim 1 wherein X is sulfur, R is methyl, R1 and R2 each is hydrogen, and n is 1.6. 